Search results for "Octatetraene"
showing 6 items of 6 documents
A theory ofnonverticaltriplet energy transfer in terms of accurate potential energy surfaces: The transfer reaction from π,π* triplet donors to 1,3,5…
2004
Triplet energy transfer (TET) from aromatic donors to 1,3,5,7-cyclooctatetraene (COT) is an extreme case of "nonvertical" behavior, where the transfer rate for low-energy donors is considerably faster than that predicted for a thermally activated (Arrhenius) process. To explain the anomalous TET of COT and other molecules, a new theoretical model based on transition state theory for nonadiabatic processes is proposed here, which makes use of the adiabatic potential energy surfaces (PES) of reactants and products, as computed from high-level quantum mechanical methods, and a nonadiabatic transfer rate constant. It is shown that the rate of transfer depends on a geometrical distortion paramet…
Theoretical Determination of the Singlet → Singlet and Singlet → Triplet Electronic Spectra, Lowest Ionization Potentials, and Electron Affinity of C…
2003
The singlet → singlet and singlet → triplet electronic spectra of cycloocta-1,3,5,7-tetraene are studied using multiconfigurational second-order perturbation theory (CASPT2) and extended atomic natural orbitals (ANOs) basis sets. The observed dipole-allowed features at 4.43, 6.02, and 6.42 eV and the spin-forbidden singlet → triplet bands with maxima at 3.05, 4.05, and 4.84 eV (Frueholz, R. P.; Kuppermann, A. J. Chem. Phys. 1978, 69, 3614) are assigned as the transitions 1 1 A 1 → 1 1 A 2 , 1 1 A 1 → 2 1 B 2 (3p z ), 1 1 A 1 → 3 1 E, and 1 1 A 1 - 1 3 A 2 , 1 1 A 1 → 1 3 E, 1 1 A 1 → 1 3 B 1 , respectively. The lowest (3s) Rydberg singlet and triplet states are placed at 5.58 (2 1 A 1 ) and…
Nature of the ring-closure process along the rearrangement of octa-1,3,5,7-tetraene to cycloocta-1,3,5-triene from the perspective of the electron lo…
2011
We analyze the behavior of the energy profile of the ring-closure process for the transformation of (3Z,5Z)-octa-1,3,5,7-tetraene 5 to (1Z,3Z,5Z)-cycloocta-1,3,5-triene 6 through a combination of electron localization function (ELF) and catastrophe theory (CT). From this analysis, concepts such as bond breaking/forming processes, formation/annihilation of lone pairs, and other electron pair rearrangements arise naturally through the reaction progress simply in terms of the different ways of pairing up the electrons. A relationship between the topology and the nature of the bond breaking/forming processes along this rearrangement is reported. The different domains of structural stability of …
Changing the size of a cavity via an electron-transfer: synthesis and reduction of 1,5,22,26-tetraoxa-[5,5]-(2,8)-dibenzo[a,e]cylooctatetraenophane
1989
Abstract The synthesis and electron transfer reactions of the title compound, the first macrocycle incorporating two cyclooctatetraene units, are described.
Die symmetrischen Cyclooctadienine: 1,5‐Cyclooctadien‐3‐in und 1,3‐Cyclooctadien‐6‐in
1985
Die Titelverbindungen 16 und 17, hoch gespannte Kohlenwasserstoffe aus der C8H8-Reihe, konnen auf sechs- bzw. siebenstufigen Synthesewegen aus 1,5-Cyclooctadien (1) bzw. Cyclooctatetraen (2) hergestellt und in reiner Form isoliert werden. Ihre Stabilitat und ihr chemisches Verhalten werden diskutiert. Dabei stehen Di- und Oligomerisierungen einerseits und Diels-Alder-Reaktionen andererseits im Vordergrund. 16 und 17 sind sehr reaktive Dienophile; 17 ist daruber hinaus auch als Dien einzusetzen. The Symmetrical Cyclooctadienynes: 1,5-Cyclooctadien-3-yne and 1,3-Cyclooctadien-6-yne Starting with 1,5-cyclooctadiene (1) and cyclooctatetraene (2), respectively, the title compounds 16 and 17, hig…
Reductive transformations - 11. stereoselective cycloannelation and bridging of the cyclooctatetraene dianionMakromol. Chem., Rapid. Commun. 1988, 9,…
1988
Abstract Bifunctional electrophiles with C4-, C6-, and C8-chains are reacted with the cyclooctatetraene dianion to selectively give novel cycloannelation and bridging products which possess a surprising stereochemistry and are useful starting compounds for further syntheses.